Production of unsaturated hydrocarbons



United States Patent 3,278,626 PRODUCTION OF UNSATURATED HYDROCARBONS Laimonis Bajars, Princeton, N.J., assignor to Petro-Tex Chemical Corporation, Houston, Tex., a corporation of Delaware No Drawing. Filed Dec. 4, 1962, Ser. No. 242,098

6 Claims. (Cl. 260-680) 1 This application is a continuation-in-part of my copending and now abandoned applications Serial Number 52,775, filed August 30, 1960, entitled Improved Dehydrogenati'on Process, which was a continuation-inpart of my application Serial No. 825,656, filed July 8, 1959, entitled Dehydrogenation Process, now abandoned, Serial Number 72,327, filed November 29, 1960, entitled Dehy-drogenation Process, Serial Number 145,992, filed October 18, 1961, entitled Dehydrogenation of Hydrocarbons, Serial Number 145,993, filed October 18, 1961, entitled Dehydrogenation Process, Serial Number 156,953, filed December 4, 1961, entitled Dehydrogenation Process, Serial Number 156,956, filed December 4, 1961, entitled Dehydrogenation, and Serial Number 196,870, filed May 23, 1962, entitled Dehydrogenation Process.

This invention relates to a process for dehydrogenating organic compounds and relates more particularly to the dehydrogenation of aliphatic hydrocarbons of 4 to 6 carbon atoms.

The dehydrogenation of aliphatic hydrocarbons such as butylenes to butadicne is accomplished commercially by passing butylenes at high temperatures over calciumnickel-phosphate or iron oxide catalysts. In the case of calcium-nickel-phosphate, butadiene is obtained from butylenes at yields of 36 to 40 percent in a cyclic, noncontinuous operation. Over iron oxide catalysts, butylenes are converted to butadiene at yields of about 19 percent. While these yields are commercial, it has been a continuing object of those skilled in the art to provide processes with higher yields of butadiene and other unsaturated hydrocarbons.

Iodine has been disclosed for use in the dehydrogenation of hydrocarbons in US. Patent 2,890,253. Large quantities of iodine are required according to this patent as the iodine is used as a reactant in the process. According to this patent, normally one atom of iodine reacts with each atom of hydrogen from the hydrocarbon being dehydrogenated. For example, in the dehydrogenation of butane to butadiene, four atoms of iodine react with four atoms of hydrogen to convert butane to butadiene. The patent suggests that the amounts of iodine required in such a reaction may be reduced by adding oxygen to the process; however, the amount of oxygen used must be no greater than one mol of oxygen per atom of iodine present. According to the examples high ratios of iodine are utilized, such as 1.3 mols of iodine per mol of hydrocarbon to be dehydrogenated. The molecular weight of iodine is 254 and this means that the dehydrogenation of butane with 1.3 mol-s of iodine, 330 pounds of iodine would be charged for each 58 pounds of butane. Because of the corrosive eliect of iodine and hydrogen iodide, such reactions have been conducted in quartz or in glass lined reactors.

I have now discovered that greatly improved yields of unsaturated hydrocarbon of 4 to 6 carbons are obtained by dehydrogenating hydrocarbons of 4 to 6 carbon atoms in vapor phase in admixture with critical ratios of oxygen and iodine and a particular class of catalysts at elevated temperatures when the partial pressure of the hydrocarbon to be dehydrogenated is equivalent to no greater than 10 inches mercury at a total pressure of approximately 30 inches of mercury absolute, or one atmosphere.

3,278,626 Patented Oct. 11, 1966 The invention is suitably carried out by reacting at a temperature of at least 400 C. the mixture of the hydrocarbon to be dehydrogenated, iodine and oxygen, with the partial pressure of the hydrocarbon to be dehydrogenated being no greater than about 10 inches mercury absolute, in contact with certain elements from the Periodic Table Group IB and HR. The catalytic elements of these groups are copper from Group IB and the elements of Group HR. The catalysts are autoregenerative and therefore the process is continuous.

Not only is the unexpectedly high selectivity and conversion 'of economic advantage for most efficient utilization of feed stock, as compared to prior art processes, but straightforward and efiicient purification of the desired butadiene-1,3 is readily accomplished because of the high yield of butadiene-l,3 and the low concentration of impurities which have to be removed. In the present commercial processes, a series of prefractionation, extractive distillation and final fractionation steps are required to isolate butadiene from process streams in sufiicient high purity for commercial use because of the low conversion of butylenes, and the resulting large amounts of difiicultto-separate impurities. An advantage of the process of this invention is that less tars and polymer are formed compared to suggested prior art processes.

According to this invention the process is conducted in the presence of an element from Group IIB, copper or compounds thereof. The groups are based on the conventional long form of the Periodic Table as the Periodic Chart found on pages 400-401 of the 39th edition (1957-58) of the Handbook of Chemistry and Physics (Chemical Rubber Publishing Company). Suitable compounds are such as elemental copper, cupric bromide, cupric chloride, cupric oxide, cupric sulfate, cuprous bromide, cuprous fluoride, cuprous iodide, cuprous oxide, cuprous silicide, zinc oxide, zinc hydroxide, zinc sulfate, zinc bromide, zinc fluoride, zinc iodide, zinc silicate, zinc phosphate, cadmium oxide (CdO), tribasic cadmium phosphate, cadmium pyrophosphate, cadmium sulfate (CdSo cadmium iodide, cadmium chloride, cadmium bromide, mercuric oxide and mixtures thereof. Under the conditions of reaction the catalytic elements will be present in inorganic form, however such compounds as cupric acetate may be charged to the reactor and decomposed to the inorganic compound under the condition of reaction. Similarly, some of the carbonates and hydroxides will be converted under the conditions of reaction. Suitable compounds are such as the oxides and salts such as the phosphates, sulfates and halides including the iodides, bromides, chlorides and fluorides. The preferred catalysts are those containing the elements copper, zinc, cadmium and compounds thereof.

A preferred feature of this invention is the use of an amount of alkali and/0r alkaline earth material incorporated with the above described compounds. Improved results such as higher yields, selectivities and conversions may be obtained by the use of such combinations. The alkali or alkaline earth compounds may conveniently be present in such forms as the oxides, hydroxides, halides or as precursors of these compounds. Under the conditions of reaction the alkali and alkaline earth compounds will be inorganic. The alkali and/ or alkaline earth atoms may also be bonded to the copper or Group IIB atoms under the conditions of reaction. The amount of alkali and/ or alkaline earth metal compounds may be varied quite widely and while small amounts as low as one-tenth weight percent have been used, much larger amounts may be employed. Generally the total amount of alkali and alkaline earth compounds will be from 0.1 to 25 weight percent of the total and will usually be between about one and ten weight percent of the combined weight of the copper or Group IIB compound and alkali and/ or alkaline Q? earth compound. On an atomic basis the atom of alkali elements and/or alkaline earth elements will ordinarily be present in an amount of between 0.025 and 0.4 atom per total atoms of Group IlB or copper. Alkali and alkaline earth compounds which are suitable are such as lithium chloride, lithium oxide, strontium oxide, potassium bromide, potassium iodide, sodium chloride, magnesium oxide, calcium oxide, barium oxide, mixtures thereof and the like.

The total pressure on systems employing the process of this invention normally will be about or in excess of atmospheric pressure, although subatmospheric pressure can be used. Higher pressures, such as about 100 or 200 p.s.i.g. may be used. However, the initial partial pressure of the hydrocarbon to be dehydrogenated is an important and critical feature of the invention. The partial pressure of the hydrocarbon to be dehydrogenated should be equivalent to below about inches mercury absolute, or /3 atmosphere, when the total pressure is one atmosphere to realize the advantages of this invention. Also because the initial partial pressure of the hydrocarbon to be dehydrogenated is equivalent to less than about 10 inches of mercury at a total pressure of one atmos phere, the combined partial pressure of the hydrocarbon to be dehydrogenated plus the dehydrogenated hydrocarbon will also be equivalent to less than about 10 inches of mercury. For example, if butene is being dehydrogenated to butadiene, at no time will the combined partial pressure of the butene and butadiene be greater than equivalent to about 10 inches of mercury at a total pressure of one atmosphere. Preferably the hydrocarbon to be dehydrogenated should be maintained at a partial pressure equivalent to less than one-third the total pressure, such as no greater than six inches or no greater than four inches of mercury, at a total pressure of one atmosphere. The desired pressure is obtained and maintained by techniques including vacuum operations, or by using helium, organic compounds, nitrogen, steam and the like, or by a combination of these methods. Steam is particularly advantageous and it is surprising that the desired reactions to produce high yields of product are effected in the presence of large amounts of steam. When steam is em ployed, the ratio of steam to hydrocarbon to be dehydrogenated is normally within the range of about 4 to 20 or 30 mols of steam per mol of hydrocarbon, and generally will be between 8 and mols of steam per mol of hydrocarbon. When air is employed as the source of oxygen, then less steam normally will be required. The degree of dilution of the reactants with steam, nitrogen and the like is related to keeping the partial pressure of hydrocarbon to be dehydrogenated in the system equivalent to preferably below 10 inches of merury at one atmosphere total pressure. For example, in a mixture of one mol of butene, three mols of steam and one mol of oxygen under a total pressure of one atmosphere the butene would have an absolute pressure of one-fifth of the total pressure, or roughly six inches of mercury absolute pressure. Equivalent to this six inches of mercury butene absolute pressure at atmospheric pressure would be butene mixed with oxygen and iodine under a vacuum such that the partial pressure of the butene is six inches of mercury absolute. A combination of a diluent such as steam together with a vacuum may be utilized to achieve the desired partial pressure of the hydrocarbon. For the purpose of this invention, also equivalent to the six inches of mercury butene absolute pressure at atmospheric pressure would be the same mixture of one mol of butene, three mols of steam and one mol of oxygen under a total pressure greater than atmospheric, for example, a total pressure of 15 or inches mercury above atmospheric. Thus, when the total pressure on the reaction zone is greater than one atmosphere, the absolute values for the pressure of butene will be increased in direct proportion to the increase in total pressure above one atmosphere. Another feature of this invention is that the combined partial pressure of the hydrocarbon to be dehydrogenated plus the iodine liberating material will also be equivalent to less than 10 inches of mercury, and preferably less than 6 or 4 inches of mercury, at a total pressure of one atmosphere. The lower limit of hydrocarbon partial pressure will be dictated by commercial considerations and practically will be greater than about 0.1 inch mercury.

The minimum amount of oxygen used generally will be from about one-fourth mol of oxygen per mol of hydrocarbon to be dehydrogenated to about 2 mols or more of oxygen per mol of hydrocarbon, as much as 5 mols have been employed. Optimum selectivity has been obtained when amounts of oxygen from about 0.25 to about 1 mol of oxygen per mol of hydrocarbon to be dehydrogenated were employed. High conversions have been obtained when the amount of oxygen was varied from about 0.75 to about 1.75 mols of oxygen per mol of hydrocarbon to be dehydrogenated. Maximum yields of unsaturated hydrocarbon product have been obtained with amounts of oxygen from about 0.4 to about 1.25 mols of oxygen per mol of hydrocarbon to be dehydrogenated, so that within the range of 0.25 or 0.35 to 1.75 mols of oxygen per mol of hydrocarbon to be dehydrogenated, economic and operational considerations will dictate the exact molar ratio of hydrocarbon to oxygen used. A particularly useful range is from about one-half to one mol of oxygen per mol of hydrocarbon to be dehydrogenated. Oxygen is supplied to the system as pure oxygen or may be diluted with inert gases such as helium, carbon dioxide and nitrogen as air. In relation to iodine, the amount of oxygen employed preferably will be greater than 2 gram mols of oxygen per gram mol of iodine and normally will be greater than 4 gram mols of oxygen per gram mol of iodine. Usually the ratio of the mols of oxygen to the mols of iodine will be'from 5 or 8 to 500 and preferably will be between 15 and 300 mols of oxygen per mol of iodine.

Iodine employed in the process of this invention may be iodine itself, hydrogen iodide, or other inorganic iodides, organic iodides or any iodine containing compound which decomposes under the reaction conditions defined herein to provide free iodine or hydrogen iodide. Such organic iodine compounds may include aliphatic iodides including alkyl iodides such as methyl iodide, ethyl iodide, propyl iodide, butyl iodide, amyl iodide, hexyl iodide, octyl iodide, iodoform and the like. Both primary, secondary and tertiary alkyl iodides may be employed. Similarly, aromatic and heterocyclic iodides may be employed, for example, phenyliodide, benzyl iodide, cyclohexyl iodide, and the like. Additional iodine compounds are iodohydrins such as ethylene iodohydrin; iodo substituted aliphatic acids such as iodoacetic acid; organic amine iodide salts of the general formula R N-HI, wherein R is a hydrocarbon radical containing from 1 to 8 carbon atoms such as methyl amine hydroiodide; volatile metalloid iodides such as AsI and other iodine compounds such as SI SI SOI I0 I 0 CHI CI and the like. Preferred, of course, among the organic iodides, for ease of handling are the alkyl iodides of l to 6 carbon atoms. Preferred are iodine and/or hydrogen iodide. It is an advantage of this invention that hydrogen iodide may be employed as the iodine source, with one advantage being that the hydrogen iodide in the eflluent from the reactor may be fed directly back to contact the hydrocarbons in the dehydrogenation reactor without any necessity of converting the hydrogen iodide to iodine. It is understood that when a quantity of iodine is referred to herein, both in the specification and the claims, that this refers to the calculated quantity of iodine in all forms present in the vapor space under the conditions of reaction regardless of the initial source or the form in which the iodine is present. For example, a reference to 0.05 mol of iodine would refer to the quantity of iodine present whether the iodine was fed as 0.05 mol of I or 0.10 mol of HI. Generally the iodine compounds will have a boiling or decomposition point or less than 400 C.

The iodine concentration normally will be varied from at least about 0.001 mol to about 0.2 mol of iodine per mol of hydrocarbon to be dehydrogenated. It is preferred to use less than 0.1 mol of iodine per mole of hydrocarbon to be dehydrogenated. Amounts of iodine between 0.005 and 0.08 or 0.09 mol of iodine per mol of hydrocarbon to be dehydrogenated are preferred. A suitable ratio is between about 0.01 and 0.05 mol of iodine per mol of hydrocarbon to be dehydrogenated. It is one of the advantages of this invention that in accordance with the defined process, very small amounts of iodine may be used in the dehydrogenation of aliphatic hydrocarbons as compared to prior art processes. Preferably the iodine will be present in an amount no greater than 5 or mol percent of the total feed to the dehydrogenation zone. Normally the iodine will be present from about 2 to 25 weight percent of the hydrocarbon to be dehydrogenated.

Hydrocarbons to be dehydrogenated according to the process of this invention are aliphatic hydrocarbons of 4 to 6 carbon atoms and preferably are selected from the group consisting of mono-olefins or diolefins of 4 to 6 carbon atoms, saturated aliphatic hydrocarbons of 4 to 5 carbon atoms and mixtures thereof. Examples of feed materials are butene-l, cis-butene-Z, transbutene-Z, Z-methyl butene-3, Z-methyl butene-l, Z-methyl butene-2, n-butane, isobutane, butadiene-l,3, methyl butane, Z-methyl pentene-l, Z-methyl pentene-2 and mixtures thereof. For example, n-butane may be converted to a mixture of butene-l and butene-Z or may be converted to a mixture of butene-l, butene-Z and/ or butadiene-l,3. A mixture of n-butane and butene-2 may be converted to butadiene-l,3 or a mixture of butadiene-l,3 together with some butene-2 and butene-l. n-Butane, butene-l, butene-Z or butadiene-1,3 or mixtures thereof may be converted to vinyl acetylene. The reaction temperature for the production of vinyl acetylene is normally within the range of about 600 C. to 1000 C. such as between 650 C. and 850 C. Isobutane may be converted to isobutylene. The Z-methyl butenes such as Z-methyl butene-l may be converted to isoprene. Excellent starting materials are the four carbon hydrocarbons such as butene-l, cisor transbutene-2, n-butane, and butadiene- 1,3 and mixtures thereof. Useful feeds as starting materials may be mixed hydrocarbon streams such as refinery streams. For example, the feed material may be the olefin-containing hydrocarbon mixture obtained as the product from the dehydrogenation of hydrocarbons. Another source of feed for the present process is from refinery by-products. For example, in the production of gasoline from higher hydrocarbons by either thermal or catalytic cracking a predominantly hydrocarbon stream containing predominantly hydrocarbons of four carbon atoms may be produced and may comprise a mixture of butenes together with butadiene, butane, isobutane, isobutylene and other ingredients in minor amounts. These and other refinery by-products which contain normal ethylenically unsaturated hydrocarbons are useful as starting materials. Another source of feedstock is the product from the dehydrogenation of butane to butenes employing the Houdry Process. Although various mixtures of hydrocarbons are useful, the preferred hydrocarbon feed contains at least 50 weight percent butene-l, butene-Z, n-butane and/or butadiene-1,3 and mixtures thereof, and more preferably contains at least 70 percent n-butane, butene-l, butene-2 and/or butadiene-l,3 and mixtures thereof. Any remainder usually will be aliphatic hydrocarbons. The process of this invention is particularly effective in dehydrogenating aliphatic hydrocarbons to provide a product wherein the major unsaturated product has the same number of carbon atoms as the feed hydrocarbon.

In the above descriptions 'of catalyst compositions, the composition described is that of the surface which is exposed in the dehydrogenation zone to the reactants. That is, if a catalyst carrier is used, the composition described as the catalyst refers to the composition of the surface and not to the total composition of the surface coating plus carrier. The catalytic compositions are intimate combinations or mixtures of the ingredients. These ingredients may or may not be chemically combined or alloyed. Inert catalyst binding agents or fillers may be used, but these will not ordinarily exceed about 50 percent or 65 percent by Weight of the catalytic surface. The weight percent of the described catalytic atoms will generally be at least 20 percent, and preferably at least 35 percent of the composition of the catalyst surface exposed to the reaction gases.

The amount of solid catalyst utilized may be varied depending upon such variables as the activity of the catalyst, the amount of iodine and oxygen used, the flow rates of reactants and the temperature of reaction. The ratio of square feet of catalyst surface per cubic foot of reaction zone containing catalyst will be at least 25 square feet of catalyst surface per cubic foot of reaction zone, such as at least 40 square feet per cubic foot of reaction zone. The catalyst is more effectively utilized when the catalyst is present in an amount of at least 75 square feet of catalyst surface per cubic foot of reaction zone containing catalyst, and preferably the ratio of catalyst surface to volume will be at least 120 square feet of catalyst surface per cubic foot of reaction zone containing catalyst Of course, the amount of catalyst surface may be much greater when irregular surface catalysts are used. When the catalyst is in the form of particles, either supported or unsupported, the amount of catalyst surface may be expressed in terms of the surface area per unit weight of any particular volume of catalyst particles. The ratio of catalytic surface to weight will be dependent upon various factors including the particle size, particle distribution, apparent bulk density of the particles, amount of active catalyst coated on the carrier, density of the carrier, and so forth. Typical values for the surface to weight ratio are such as about /2 to 200 square meters per gram, although higher and lower values may be used.

Excellent results have been obtained by packing the reactor with catalyst particles as the method of introducing the catalytic surface. The size of the catalyst particles may vary widely but generally the maximum particle size will at least pass through a Tyler Standard Screen which has an opening of 2 inches, and generally the largest particles of catalyst will pass through a Tyler Screen with one inch openings. Very small particle size carriers may be utilized with the only practical objection being that extremely small particles cause excessive pressure drops across the reactor. In order to avoid high pressure drops across the reactor generally at least 50 percent by Weight of the catalyst will be retained by a 10 mesh Tyler Standard Screen which has openings of inch. However, if a fluid bed reactor is utilized, catalyst particles may be quite small, such as from about 10 to 300 microns. Thus, the particle size when particles are used preferably will be from about 10 microns to a particle size which will pass through a Tyler Screen with openings of 2 inches. If a carrier is used the catalyst may be deposited on the carrier by methods known in the art such as by preparing an aqueous solution or dispersion of the catalyst compound, mixing the carrier with the solution or dispersion until the active ingredients are coated on the carrier. The coated particles may then 'be dried, for example, in an oven at a temperature of greater than C. Various other methods of catalyst preparation known to 1 As measured by the Innes nitrogen absorption method on a representative unit volume of catalyst particles. The Innes method is reported in W. B.

Innes Anal. Chem., 23, 759

those skilled in the art may be used. When carriers are utilized, these will be approximately of the same size as the final coated catalyst particle, that is, for fixed bed processes the carriers will generally be retained on 10 mesh Tyler Screen and will pass through a Tyler Screen with openings of 2 inches. Very useful carriers are silicon carbide, asbestos, and the like. When carriers are used, the amount of catalyst on the carrier will generally be in the range of about 5 to 75 weight percent of the total weight of the active catalytic material plus carrier. The carriers maybe of a variety of shapes, including irregular shapes, cylinders or spheres. Other methods may be utilized to introduce the catalytic surface such as by the use of rods, w-ires, mesh or shreds and the like of catalytic material. The technique of utilizing fluid beds lends itself well to the process of this invention.

The temperature at which the reaction is conducted is from above 400 C. or 450 C. to temperatures as high as 800 C. or 1000 C. or higher. Excellent results are ordinarily obtained Within the range of about 425 C. to about 800 C. or 850 C. Butadiene-1,3 has been obtained in good yield from butene at about 550 C. to about 750 C., and isoprene has been obtained in good yield from methyl butene at temperatures from about 425 C. to 550 C. or 625 C. Vinyl acetylene is produced in good yields from butane, butene-1, butene-2, butadiene-1,3 and mixtures thereof at temperatures above 600 C., such as above 650 C. The temperatures are measured at the maximum temperature in the reactor. An advantage of this invention is the extremely wide latitude of reaction temperatures.

The flow rates of the gaseous reactants may be varied quite widely and can be readily established by those skilled in the art. Good results have been obtained with flow rates of the hydrocarbon to be dehydrogenated ranging from about one-fourth to three or higher liquid volumes of hydrocarbon to be dehydrogenated per volume of reactor containing catalyst per hour. Generally, the flow rates will be within the range of about 0.10 to 25 or higher liquid volumes of the hydrocarbon to be dehydrogenated, calculated at standard conditions of 25 C. and 760 mm. of mercury per volume of reactor space containing catalyst per hour (referred to as either LHSV or liquid v./v./hr.). Usually the LHSV will be between 0.15 and 15. The volume of reactor containing catalyst is that volume of reactor space excluding the volume displaced by the catalyst. For example, if a reactor has a particular volume of cubic feet of void space, when that void space is filled with catalyst particles the original void space is the volume of reactor containing catalyst for the purpose of calculating the flow rates. The residence or contact time of the reactants in the reaction zone under any given set of reaction conditions depends upon all the factors involved in the reaction. Contact times ranging from about 0.1 to about 5 to seconds have been found to be satisfactory. However, a wider range of residence times may be employed which may be as low as about 0.001 or 0.01 second to as long as several minutes, as high as about 3 minutes, although such long reaction times are not preferred. Normally, the shortest contact time consonant with optimum yields and operating conditions is desired. Residence time is the calculated dwell time of the reaction mixture in the reaction zone assuming the mols of product mixture are equivalent to the mols of feed mixture. For the purpose of calculation of residence times the reaction zone is the portion of the reactor packed with the catalyst.

A variety of reactor types may be employed. For example, tubular reactors may be employed. Fixed bed reactors containing the catalysts in the form of grids, screens, pellets, with or without supports and the like may also be used. In any of these reactors suitable means for heat control should be provided. Fluid and moving bed systems are readily applied to the processes of this invention.

The manner of mixing the iodine or iodine compound, the hydrocarbon to be dehydrogenated, oxygen, and steam, if employed, is subject to some choice. In normal operations the hydrocarbon to be dehydrogenerated may be preheated and mixed with steam and preheated oxygen or air and iodine or hydrogen iodide are mixed therewith prior to passing the stream in vapor phase over the catalyst bed. Hydrogen iodide or a source of iodine may be dissolved in water and may be mixed with steam or air prior to reaction. Any of the reactants may be split and added incrementally. For example, part of the iodine may be mixed with the hydrocarbon to be de hydrogenated and the oxygen. The mixture may then be heated to effect some dehydrogenation and thereafter the remainder of the iodine added to effect further dehydrogenation. The reactor may be of any type. Conventional reactors used for the preparation of unsaturated hydrocarbons are satisfactory and the reactor may be packed or unpacked. The effluent reaction product from the reactor is cooled and then passed to means for removing iodine such as in a caustic scrubber. The hydrocarbon product is then; suitably purified as by fractionation to obtain the desired high purity unsaturated product. The effluent reaction product from the reactor may then be cooled and passed to means for removing hydrogen iodide which normally will represent much of the iodine present during the course of the reaction, and the hydrocarbon product is then suitably purified as by fractionation to obtain the desired high purity butadiene or isoprene.

According to this invention the catalyst is autoregenerative and thus the process is continuous. Little or no energy input is required for the process and it may be operated essentially adiabatically. Moreover, small amounts of tars and polymers are formed as compared to prior art processes suggesting the use of large amounts of iodine.

In the following examples will [be found specific embodiments of the invention and details employed in the practice of the invention. Percent conversion refers to the mols of olefin consumed per 100 mols of olefin fed to the reactor, percent selectivity represents the mols of diolefin formed per 100 mols of olefin consumed, and percent yield refers to the mols of diolefin formed per mol of olefin fed. All quantities of iodine expressed are calculated as mols of I Example 1 A Vycor 1 reactor which was filled with Vycor 1 Raschig rings having deposited thereon copper phosphate was heated by means of an external electric furnace. At a 700 C. furnace temperature, in a series of runs, a butene-2 flow rate was maintained at 1 liquid v./v./hr., mixed with oxygen and steam at mol ratios of butene to steam to oxygen of 1 to 16 to 0.85. Hydrogen iodide was added as concentrated 47 .percent acid at 3.75 cubic centimeters per hour which was equivalent to 0.017 mol of iodine per mol of butene-2. When the reactor was filled with clean Vycor Raschig rings and operated as described a yield of butadiene-1,3 of 24 percent was obtained. When this reaction was repeated in the absence of hydrogen iodide, the yield of butadiene obtained was 18 percent. The reactor was then filled with Vycor Raschig rings having deposited thereon the copper phosphate. The results obtained were a conversion of butene-2 of 94 mol percent, a selectivity of 81 mol percent for a yield of butadiene of 76 mol percent.

Example 2 When the procedure of Example 1 was repeated with cupric oxide as the catalyst the butene-2 was converted to butadiene with the percent conversion of butene-2 being 80 percent.

The Vycor of this and the following examples is a 96 percent silica glass.

When the above procedure was repeated with zinc oxide as the catalyst the butene-Z was converted to butadiene with the percent conversion of butene-Z being 70 percent.

Example 3 A thin coating of zinc oxide was deposited on the walls of a quartz reactor. The coating was accomplished by filling the reactor at room temperature with an aqueous solution of zinc nitrate, draining and drying in a gentle air stream while gradually raising the temperature to about 450 C.

2-methyl butene-2 was dehydrogenated to isoprene at a maximum temperature in the reactor of 550 C. The flow rate of 2-methyl butene-2 was 0.11 liter per minute, calculated as the liquid volume at 760 mm. of mercury and 25 C. The flow rate was equivalent to /2 liquid v./v./hr. The ratio of steam to Z-methyl butene-2 was 10/ 1, and the ratio of iodine (calculated as I to Z-methyl butene-2 was 0.04. The ratio of oxygen (fed as pure oxygen) to 2-methyl butene-Z was 1/1. Under these conditions isoprene was produced at a percent selectivity of 94 percent.

Example 4 Is-oprene was produced from 2-methyl butene-2 with a metallic copper catalyst utilizing ratios of 0.03 1 1.0 oxygen and 20 steam per mol of 2-methyl butene-Z. The flow rate was /2 liquid v./v./hr. The catalyst was a bundle of A inch outside diameter copper tubing inside the reactor. High selectivities and yields were produced. When the copper catalyst was removed from the reactor the yield was cut approximately in half. I

From the foregoing description of the invention, it will be seen that a novel and greatly improved process for producing unsaturated hydrocarbons is provided. Other examples could be devised for a process whereby the catalyst contained the described elements; preferably with the described elements constituting greater than or at least fifty atomic weight percent of any metal atoms in the surface exposed to the reaction gases. Although representative embodiments of the invention have been specifically described, it is not intended or desired that the invention be limited solely thereto since it will be apparent to those skilled in the art that modifications and variations may be made without departing from the spirit and scope of the invention.

I claim:

1. The method for dehydrogenating aliphatic hydrocarbons which comprises heating in the vapor phase at a temperature greater than 400 C. an aliphatic hydrocarbon of 4 to 6 carbon atoms with oxygen in a molar ratio of 0.35 to 1.75 mols of oxygen per mol of said aliphatic hydrocarbon, from at least about 0.001 to 0.08 mol of iodine per mol of said aliphatic hydrocarbon, the initial partial pressure of said aliphatic hydrocarbon being equivalent to no greater than about 10 inches of mercury at one atmosphere total pressure, with a catalyst comprising copper phosphate, with the said copper phosphate constituting greater than fifty atomic weight percent of any metal atoms in the surface exposed to the reaction gases, the ratio of the mols of said oxygen to the mols of said iodine being greater than four.

2. The method for preparing aliphatic diolefins which comprises heating in the vapor phase at "a temperature of about 400 C. to about 800 C. a mono-ethylenically unsaturated hydrocarbon of 4 to 6 carbon atoms with oxygen in a molar ratio of 0.35 to 1.75 mols of oxygen per mol of said unsaturated hydrocarbon, from .005 to 0.08 mol of iodine per mol of said unsaturated hydrocarbon the initial pressure of said unsaturated hydrocarbon being equivalent to less than one-third atmosphere atone atmosphere total pressure, with a catalyst comprlsing copper phosphate, the copper of the said copper phosphate constituting greater than fifty atomic weight percent of any metal atoms in the surface exposed to the reaction gases, the ratio of the mols of said oxygen to the mols of said iodine 'being greater than four. 5 The method for preparing butadiene-1,3 which comprises heating in the vapor phase at a temperature of about 400 C. to about 800 C. n-butene with oxygen in a molar ratio of 0.35 to 1.75 mols of oxygen per mol of said unsaturated hydrocarbon, from .005 to 0.08 mol of iodine per mol of said unsaturated hydrocarbon, the initial pressure of said unsaturated hydrocarbon being equivalent to less than one-third atmosphere at one atmosphere total pressure, with a catalyst consisting essentially of copper phosphate, the ratio of the mols of said oxygen to the mols of said iodine being greater than four.

4. The method for preparing aliphatic diolefins which comprises heating in the vapor phase at a temperature of about 400 C. to about 800 C. a mono-ethylenically unsaturated hydrocarbon of 4 to 6 carbon atoms with oxygen in a molar ratio of 0.35 to 1.75 mols of oxygen per mol of said unsaturated hydrocarbon, from .005 to 0.08 mol of iodine per mol of said unsaturated hydrocarbon, the initial pressure of said unsaturated hydrocarbon being equivalent to less than one-third atmosphere at one atmosphere total pressure, with a catalyst comprising copper, the said copper constituting greater than fifty atomic weight percent of any metal atoms in the surface exposed to the reaction gases, the ratio of the mols of said oxygen to the mols of said iodine being greater than four.

5. The method for preparing aliphatic diolefins which comprises heating in the vapor phase at a temperature of about 400 C. to about 800 C. a mono-ethylenically unsaturated hydrocarbon of 4 to 6 carbon atoms with oxygen in a molar ratio of 0.35 to 1.75 mols of oxygen per mol of said unsaturated hydrocarbon, from .005 to 0.08 mol of iodine per mol of said unsaturated hydrocarbon, the initial pressure of said unsaturated hydrocarbon being equivalent to less than one-third atmosphere at one atmosphere total pressure, with a catalyst comprising copper oxide, the copper of said copper oxide constituting greater than fifty atomic weight percent of any metal atoms in the surface exposed to the reaction gases, the ratio of the mols of said oxygen to the mols of said iodine being greater than four.

6. The method for preparing aliphatic diolefins which comprises heating in the vapor phase at a temperature of about 400 C. to about 800 C. a mono-ethylenically unsaturated hydrocarbon of 4 to 6 carbon atoms with oxygen in a molar ratio of 0.35 to 1.75 mols of oxygen per mol of said unsaturated hydrocarbon, from .005 to 0.08 mol of iodine per mol of said unsaturated hydrocarbon, the initial pressure of said unsaturated hydrocarbon being equivalent to less than one-third atmosphere at one atmosphere total pressure, with a catalyst comprising zinc oxide, 55 the zinc of the said zinc oxide constituting greater than fifty atomic weight percent of any metal atoms in the surface exposed to the reaction gases, the ratio of the mols of said oxygen to the mols of said iodine being greater PAUL M. COUGHLAN, JR., Primary Examiner. ALPHONSO D. SULLIVAN, Assistant Examiner. 

1. THE METHOD FOR DEHYDROGENATING ALIPHATIC HYDROCARBONS WHICH COMPRISES HEATING IN THE VAPOR PHASE AT A TEMPERATURE GREATER THAN 400*C. AN ALIPHATIC HYDROCARBON OF 4 TO 6 CARBON ATOMS WITH OXYGEN IN A MOLAR ALIPHATIC OF 0.35 TO 1.75 MOLS OF OXYGEN PER MOL OF SAID ALIPHATIC HYDROCARBON, FROM AT LEAST ABOUT 0.001 TO 0.08 MOL OF IODINE PER MOL OF SAID ALIPHATIC HYDROCARON, THE INITIAL PARTIAL PRESSURE OF SAID ALIPHATIC HYDROCARBON BEING EQUIVALENT TO NO GREATER THAN ABOUT 10 INCHES OF MERCURY AT ONE ATMOSPHERE TOTAL PRESSURE, WITH A CATALYST COMPRISING COPPER PHOSPHATE, WITH THE SAID COPPER PHOSPHATE CONSTITUTING GREATER THAN FIFTY ATOMIC WEIGHT PERCENT OF ANY METAL ATOMS IN THE SURFACE EXPOSED TO THE REACTION GASES, THE RATIO OF THE MOLS OF SAID OXYGEN TO THE MOLS OF SAID IODINE BEING GREATER THAN FOUR. 